EP3950663A1 - Neues verfahren zur gewinnung von diesterverbindungen, die zur herstellung neuer quartärer ammoniumverbindungen nützlich sind - Google Patents

Neues verfahren zur gewinnung von diesterverbindungen, die zur herstellung neuer quartärer ammoniumverbindungen nützlich sind Download PDF

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EP3950663A1
EP3950663A1 EP20189198.3A EP20189198A EP3950663A1 EP 3950663 A1 EP3950663 A1 EP 3950663A1 EP 20189198 A EP20189198 A EP 20189198A EP 3950663 A1 EP3950663 A1 EP 3950663A1
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epoxide
formula
reaction
mol
item
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French (fr)
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Olivier BACK
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Rhodia Operations SAS
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Rhodia Operations SAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/22—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated the carbon skeleton being further substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/26—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having more than one amino group bound to the carbon skeleton, e.g. lysine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
    • C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring

Definitions

  • the present invention relates to a new method for obtaining diester compounds which can be used for the manufacture of new quaternary ammonium compounds, and to such new quaternary ammonium compounds.
  • WO 97/08284 discloses compositions comprising Guerbet alcohol betaine esters which are represented by the general formula
  • R 1 to R 3 are independently selected from C 1 to C 4 alkyl groups or C 2 -C 4 alkenyl groups
  • a is from 1 to 4
  • R 4 and R 5 are independently selected from C 12 to C 22 alkyl or alkenyl groups, the sum of chain lengths of R 4 and R 5 preferably being at least 30.
  • EP 721 936 and DE 3402146 relate to quaternary ammonium compounds.
  • the compounds comprise two long chain substituents which are esters of Guerbet acids.
  • novel ionic compounds in accordance with the present invention have the general formula (I) wherein
  • the aliphatic groups R are advantageously chosen from alkyl groups, alkenyl groups, alkanedienyl groups, alkanetrienyl groups and alkynyl groups.
  • the aliphatic groups R may be linear or branched.
  • the aliphatic groups R are independently chosen from alkyl and alkenyl groups.
  • the aliphatic groups R are independently chosen from alkyl and alkenyl groups, generally from C 6 -C 24 alkyl and C 6 -C 24 alkenyl groups, very often from C 6 -C 21 alkyl and C 6 -C 21 alkenyl groups and often from (i) C 6 -C 19 alkyl and C 6 -C 19 alkenyl groups or from (ii) C 6 -C 17 alkyl and C 6 -C 17 alkenyl groups.
  • R represent an alkyl group, generally a C 6 -C 24 alkyl group, very often a C 6 -C 21 alkyl group, often a C 6 -C 19 alkyl group or a C 6 -C 17 alkyl group.
  • Aliphatic groups, in particular alkyl groups, with 10 to 20, preferably with 11 to 17 or with 10 to 17 carbon atoms have been found advantageous in certain cases.
  • Acyclic aliphatic groups, more preferably linear aliphatic groups, still more preferably linear alkyl groups may be mentioned as preferred examples of substituents R.
  • the number of carbon atoms of R can be even or odd and each group R can have the same number of carbon atoms or the number of carbon atoms of different groups R may be different.
  • R', R" and R' which may be the same or different, are preferably hydrogen or a C 1 to C 4 alkyl group, preferably methyl or ethyl, more preferably methyl.
  • Preferably at least one, more preferably at least two, more preferably all three of R', R" and R'" are a C 1 to C 4 alkyl group, preferably methyl or ethyl, most preferably methyl.
  • Y is preferably an acyclic divalent aliphatic group, more preferably a linear divalent aliphatic group, still more preferably a linear alkanediyl (alkylene) group and has 1 to 6, preferably 1 to 4 carbon atoms.
  • Aliphatic group Y preferably has at least two carbon atoms, in particular 2 to 6 carbon atoms.
  • the ionic compounds in accordance with the present invention can be obtained by a variety of methods.
  • a suitable process for the manufacture of internal ketones following this route is diclosed in US 2018/0093936 to which reference is made for further details.
  • the compounds of formula (I) can preferably be obtained by two processes.
  • the first process starts with a Piria ketonization followed by hydrogenation, dehydration, epoxydation (to obtain an epoxide), hydration (to obtain a diol) and esterification (to obtain a certain diester).
  • This is a multi-step process plugged on Piria technology. It has the advantage of being salt-free and relying on chemical transformations which can be easily performed.
  • the esterification step may be followed by an amine condensation step (as the final step) to convert the diester into a compound complying with formula (I).
  • the basic reaction in the first step is:
  • the hydrogenation reaction is conducted by contacting the internal ketone with hydrogen in an autoclave reactor at a temperature ranging from 15°C to 300°C and at a hydrogen pressure ranging from 1 bar to 100 bars. Details of this process step can e.g. be found in US patent 10035746 to which reference is made here.
  • the alcohol thus obtained is subjected to dehydration to obtain an internal olefin.
  • This reaction can also be carried out under standard conditions known to the skilled person for respective dehydration reactions (e.g. US patent 10035746 , example 4) so that no further details need to be given here:
  • the epoxide can be directly engaged in next step without further purification.
  • This next step can be a hydration step (so as to form a diol, to be the followed by an esterification step) or a direct esterification step.
  • the epoxide can thereafter be hydrated to the respective diol in accordance with the following scheme:
  • the ring opening reaction can be performed by contacting the epoxide with water, generally in the presence of a suitable catalyst and at a temperature ranging generally from 15°C to 150°C.
  • a suitable catalyst for example, Bronsted or Lewis acid catalysts.
  • the diol can be esterified according to the following reaction scheme: wherein
  • esterification is first performed by contacting the diol with an esterification agent which is a carboxylic acid or an ester of a carboxylic acid of general formula: [L-Y-CO 2 R*****] (t-1)- [U u+ ] (t-1)/u
  • Y is a divalent hydrocarbon radical containing between 1 and 6 carbon atoms, more precisely a divalent C 1 -C 6 aliphatic radical, and wherein L is a leaving group.
  • Y is preferably an acyclic divalent aliphatic group, more preferably a linear divalent aliphatic group, still more preferably a linear alkanediyl (alkylene) group.
  • Y has preferably from 1 to 6, more preferably from 1 to 4 carbon atom(s), still more preferably 1 or 2 carbon atom(s). The most preferred Y is -CH 2 -.
  • esterification is performed by contacting the diol with a carboxylic acid or an ester of a carboxylic acid of formula: L-Y-CO 2 R*****.
  • a cation noted U u+ (with u preferably being 1, 2 or 3, even more preferably 1) must be present in the reactant to ensure the electroneutrality (in this case the cation possesses a u + charge).
  • This cation may e.g. be selected from H + , alkaline metal cations, alkaline earth metal cations (e.g. Na + , K + , Ca 2+ ), Al 3+ and ammonium, to mention only a few examples.
  • the nature of the leaving group L is not particularly limited provided next reaction step (i.e. amine condensation, as will be detailed later on) can occur.
  • the leaving group L is preferably chosen from:
  • t is sodium carboxymethylsulfate acid in which [L-Y-COOR*****] (t-1)- [U u+ ] (t-1)/u is [Na + ] [O-SO 2 -O-CH 2 -COOR*****] - with R***** being H, U being Na and thus [U u+ ] t/u [L t- ] being Na 2 SO 4
  • the esterification can preferably be conducted at a temperature ranging from 50°C to 250°C in the presence of an optional solvent. However the presence of such solvent is not mandatory and the reaction can be also conducted without any added solvent.
  • suitable solvents one can mention: toluene, xylene, hydrocarbons, DMSO, Me-THF, THF or mixtures thereof.
  • Water that is formed as a by-product during the reaction can be removed from the reaction medium by distillation over the course of the reaction.
  • a catalyst can also be employed during the reaction and suitable catalysts are Bronsted or Lewis acid catalysts.
  • suitable catalysts include H 2 SO 4 , para -toluenesulfonic acid, trifluoromethanesulfonic acid (commonly referred to as triflic acid), HCl, or heterogeneous acidic resins such as Amberlite ® resins, AlCl 3 etc.
  • the desired diester can be recovered after appropriate work-up and the skilled person is aware of representative techniques so that no further details need to be given here.
  • the diester of formula (III) can be easily converted into a compound of formula (I) as previously represented, which exhibits outstanding surfactant properties.
  • the epoxide can be directly esterified into the diester of formula (III) when and only when a carboxylic acid is used as the esterification agent [L-Y-CO 2 R*****] (t-1)- [U u+ ] (t-1)/u , that is to say when the esterification agent [L-Y-CO 2 R*****] (t-1)- [U u+ ] (t-1)/u is of the formula [L-Y-CO 2 H] (t-1)- [U u+ ] (t-1)/u , wherein L, Y, t, U u+ and u are as described here before in connection with the esterification of the diol.
  • the epoxide ring-opening and esterification are performed by reacting the epoxide with a carboxylic acid of general formula: [L-Y-CO 2 H] (t-1)- [U u+ ] (t-1)/u wherein L is a leaving group, Y is a divalent C 1 -C 6 aliphatic radical, t is an integer which is equal to 1 or which is equal or superior to 2, U u+ is a cation, and u is an integer fixing the positive charge of the cation.
  • esterification is performed by contacting the epoxide with a carboxylic acid of formula: L-Y-CO 2 H.
  • the diester compound of formula (III) can be converted into the ionic compound of formula (I) through the following reaction scheme: wherein
  • the amine condensation reaction is performed by contacting the intermediate diester obtained as described above with an amine of general formula NR'R"R'" where R', R" and R'" are C 1 to C 4 alkyl groups, preferably methyl or ethyl, most preferably methyl.
  • the reaction can be conducted at a temperature ranging from 15°C to 250°C in the presence of a suitable solvent.
  • a suitable solvent one can mention: THF, Me-THF, methanol, ethanol, isopropanol, DMSO, toluene, xylene or their mixture.
  • the reaction can be also conducted in the absence of any added solvent.
  • L (t-1)- plays the role of the leaving group.
  • L t- becomes then the counter-anion of the final quaternary ammonium compound.
  • the leaving group already carries a negative charge in the diester reactant (this is the case when (t-1) is equal or superior to 1 or when t is equal or superior to 2)
  • there is also formation of a salt as the by-product of the reaction with the general chemical formula [U u+ ] t/u [L t- ] as shown in the equation scheme above).
  • the compounds of formula (I) are advantageously used as surfactants. They possess indeed a particularly interesting and advantageous property profile of surfactant properties on one hand and biodegradability properties on the other hand. Biodegradability is becoming more and more an important aspect for surfactant products.
  • adsorption of a cationic surfactant on negatively charged surfaces is also an important property for such surfactants. This property is usually linked to the minimum concentration of surfactant needed to produce aggregation of a negatively charged cellulose nanocrystal (CNC, which is often used as reference material)) suspension in aqueous media. Consecutive variation of size can be monitored and followed by dynamic light scattering (DLS). Following the protocol described in E.K. Oikonomou et al., J. Phys. Chem.
  • biodegradability of the compounds of the present invention can be determined in accordance with procedures described in the prior art and known to the skilled person. Details about one such method, OECD standard 301, are given in the experimental section hereinafter.
  • Example 1 First synthesis of a quaternary di-ammonium compound starting from 16-hentriacontanone
  • 16-hentriacontanone was purchased from TCI, but could have been obtained from palmitic acid following Piria ketonization, for example in accordance with the protocol described in US patent 10035746 , chain of examples 2 to 4.
  • the reaction was performed under 20 bar hydrogen pressure. 4 nitrogen purges are performed followed by 3 purges of hydrogen at 20 bars.
  • the temperature of the reaction mixture was then set at 100°C to melt the ketone substrate. The temperature was left at 100°C during 10 min and stirring was slowly started at 200 rpm. When proper stirring was confirmed, the stirring rate was increased at 1200 rpm and the temperature was set at 150°C.
  • the reaction was conducted under an inert argon atmosphere.
  • a mechanical stirrer (A320-type stirring mobile manufactured by 3D-printing with Inox SS316L), a condenser connected to a 50 mL two-neck distillate collection flask and a temperature probe were added:
  • reaction media was then increased to 150°C to melt the alcohol and stirring was started (about 500 rpm). Finally the temperature was set-up at 300°C and the mixture was allowed to stir at 1000 rpm under argon. Reaction progress was monitored thanks to NMR analysis with a borosilicate glass tube.
  • the reaction was conducted under an inert argon atmosphere.
  • a double-jacketed 1L reactor equipped with a mechanical stirrer (propeller with four inclined plows), a condenser and a temperature probe were added 92.4 g of C 31 alkene (0.212 mol), followed by 18.2 mL (19.1 g, 0.319 mol) of acetic acid and 27.7 g (30 wt%) of Amberlite ® IR 120H resin.
  • the mixture was heated to 75°C in order to melt the fatty alkene.
  • the agitation was then started and 32.6 mL (36.1 g, 0.319 mol) of aqueous H 2 O 2 30% were slowly added into the mixture using an addition funnel while reaction mass temperature was monitored to avoid temperature increase.
  • the addition required about one hour.
  • the reaction was conducted under an inert argon atmosphere in a 500 mL three necked round bottom flask equipped with a magnetic stirrer, a heater, a condenser, a temperature probe and an insulated addition funnel.
  • a magnetic stirrer In the round bottom flask itself were added 128.7 g of chloroacetic acid (1.35 moles, 8 eq).
  • a condenser In the insulated addition funnel maintained at 65°C were added 77.8 g of melted fatty epoxide (98 wt% purity, 0.169 moles, 1 eq).
  • the first step of intermediate hydroxyl-ester formation was conducted at 65°C by the slow addition of the fatty epoxide into chloroacetic acid in order to limit the formation of ketone and epoxide self-condensation by-products.
  • the fatty epoxide was therefore added drop-wise over 30 minutes into the reactor containing chloroacetic acid at 65°C under stirring.
  • the mixture was allowed to stir at 140°C during 3h30 under vacuum (800 mbar) in order to remove water formed as a by-product during the esterification reaction.
  • the product could be easily purified by dissolving the oil in ethanol (the starting ketone being not soluble in ethanol) followed by a filtration over celite. The filtrate was evaporated to afford 94 g of black oil with a purity of 89 wt% for the bis-ester corresponding to a isolated yield of 80 % (RMN).
  • the reaction was conducted under an inert argon atmosphere in a 500 mL three necked round bottom flask equipped with a magnetic stirrer, a heater, a condenser, a temperature probe and an insulated addition funnel.
  • a magnetic stirrer In the round bottom flask itself were added 85.63 g of chloroacetic acid (0.897 mol, 5 eq).
  • a condenser In the insulated addition funnel were added 83.3 g of melted fatty epoxide (97 wt% purity, 0.179 mol, 1 eq).
  • the first step of monoester formation was conducted at 65°C without triflic acid to limit the formation of ketone and dehydration by-products.
  • the fatty epoxide was therefore added drop-wise over 2h into the reactor containing chloroacetic acid at 65°C under stirring in order to limit the self-condensation of fatty epoxide.
  • the mixture was left at 65°C under stirring during an additional hour. NMR analysis showed a conversion level >99 % for the starting epoxide.
  • the vacuum was then increased to 800 mbar and progressively until 10 mbar in order to distil chloroacetic acid, triflic acid catalyst and to complete conversion of mono-ester toward bis-ester.
  • reaction mixture was heated at 40°C and stirring was started at 1000 rpm. After 6h, NMR analysis in d 4 -MeOH showed a conversion level >99 % for the starting bis-ester with a molar composition of ⁇ 86 mol% for glycine betaine bis-ester.
  • the reactor was drained, rinsed with CH 2 Cl 2 and the volatiles were evaporated under vacuum.
  • the brown solid was reduced into a powder, deposited on a sinter filter and washed 5 times with 200 mL of ethyl acetate. The solid was dried under vacuum.
  • the product was transferred into a 1L reactor equipped with a mechanical stirrer, a condenser, a heater and a temperature probe.
  • the product was solubilized into 800 mL of chloroform and 150 g of activated charcoal pellets were added. The mixture was stirred at 40°C for 2 hours in order to whiten the product.
  • the reaction was conducted under an inert argon atmosphere in a 200 mL quartz reactor equipped with a heating mattress, a mechanical stirring (A320-type stirring mobile manufactured by 3D-printing with Inox SS316L), an insulated addition funnel, a distillation apparatus and a temperature probe.
  • reaction mixture was then raised to 250°C and once the temperature had reached 150°C, the stirring was started (1200 rpm). After 1h15 reaction time at 250°C, FTIR analysis showed complete conversion of the starting fatty acids into the intermediate magnesium carboxylate complex.
  • the temperature of the reaction mass was then raised further to 330°C and the mixture was allowed to stir at this temperature during 1h30 in order to allow decomposition of the magnesium complex to the desired ketone.
  • the temperature of the reaction mixture was allowed to cool down at 60°C and the crude was solubilized in 350 mL of hot CHCl 3 (60°C).
  • the suspension was filtered on a plug of silica (100 g) and the product was further eluted with additional amounts of CHCl 3 . After solvent evaporation 50.5 g of crude product were obtained.
  • the product was washed 3 times with 200 mL of isopropanol on a sintered filter in order to remove trace of by-products.
  • the solid was dried to afford the desired ketone as a white powder with a purity of 100 mol% corresponding to a yield of 90%.
  • the reaction was conducted under an inert argon atmosphere.
  • a mechanical stirrer (A320-type stirring mobile manufactured by 3D-printing with Inox SS316L), surmounted by a condenser connected to a 50 mL two-necked distillate collection flask and a temperature probe were added:
  • the reaction medium was first heated at 150°C in order to melt the fatty alcohol mixture and stirring was started (about 500 rpm). Then, the temperature was increased up to 300°C and the mixture was allowed to stir at 1000 rpm under argon atmosphere. The reaction progress was monitored thanks to NMR analysis. After 2 hours reaction time at 300°C, NMR analysis in CDCl 3 showed complete conversion of the fatty alcohol and also presence of 0.3 mol% of ketone which had been formed as a by-product.
  • the reaction was conducted under an inert argon atmosphere in a 500 mL three necked round bottom flask reactor equipped with a magnetic stirrer, a heater, a condenser, a temperature probe and an insulated addition funnel.
  • a 500 mL three necked round bottom flask reactor equipped with a magnetic stirrer, a heater, a condenser, a temperature probe and an insulated addition funnel.
  • 39.19 g of chloroacetic acid 410.5 mmol, 5 eq
  • In the insulated addition funnel maintained at 65°C were added 38.6 g of melted fatty epoxide (purity: 99 wt%, 82.1 mmol, 1 eq).
  • the first step of hydroxyl-ester formation was conducted at 65°C to limit the formation of ketone and dehydration by-products.
  • the fatty epoxide was therefore added drop-wise over 1h30 into the reactor containing chloroacetic acid at 65°C under stirring in order to limit the self-condensation of two fatty epoxide molecules.
  • the mixture was allowed to stir at 65°C during 30 min. NMR analysis showed a conversion level >98 % for the starting epoxide.
  • the condenser was replaced by a curved distillation column and the mixture was allowed to stir at 140°C during 5h30 under a light vacuum (975 mbar) in order to assist the removal of water which was formed as a by-product of the esterification reaction.
  • NMR analysis showed a selectivity (monoester + bis-ester) of 92 mol% and the following approximate crude mixture composition: 90 mol% of bis-ester, 2 mol% of mono-ester, 1 mol% of esterified dimer and 2 mol% of ketone.
  • the pressure was then decreased down to 800 mbar and progressively until 10 mbar in order to distil the excess of chloroacetic acid and to complete conversion of mono-ester toward bis-ester. Once the whole amount of chloroacetic acid had been distilled out (verified by NMR analysis), the mixture was cooled down to room temperature and the atmospheric pressure was re-established. The crude oil was then transferred into a flask for purification.
  • the product could be easily purified by dissolving the oil in 300 mL of isopropanol (the starting ketone being not soluble in isopropanol) followed by a filtration over celite. The filtrate was evaporated to afford 49.1 g of a black oil with a purity of 93 wt% for the bis-ester corresponding to an isolated yield of 86 % (RMN).
  • reaction mixture was then stirred (1000 rpm) at 40°C. After 3h, the mixture was allowed to cool down at room temperature and stirred overnight. The next day, NMR analysis (d 4 -MeOD) showed a full conversion of the starting bis-ester with an approximate selectivity of 92 mol% (NMR) toward the desired product glycine betaine bis-ester.
  • the reactor was drained, rinsed with THF and the volatiles were removed under vacuum.
  • the product was reduced to a powder, deposited on a sinter filter and washed 5 times with 100 mL of ethyl acetate in order to remove the organic impurities.
  • the solid was dried under vacuum to afford 53 g of a brown wax with the following approximate weight composition: 94 wt% of NQ19 quaternary bis-ammonium, 2 wt% of quaternary mono-ammonium, 0.1 wt% of N(Me) 3 .HCl and 3.5 wt% of an ether by-products.
  • the purified yield of the glycine betaine bis-ester was 94%.
  • the reaction was conducted under an inert argon atmosphere.
  • the mixture was allowed to stir a second night at 75°C.
  • the reaction was conducted under an inert argon atmosphere.
  • the mixture was allowed to stir at room temperature and 73 mL of a 3 M aqueous solution of H 2 SO 4 was then added.
  • the reaction medium was then stirred at 80°C during 90 minutes. NMR analysis showed that the reaction was completed.
  • the biphasic mixture was allowed to cool down to room temperature and the organic phase was separated.
  • the solvent was then removed under vacuum and the residue was suspended in 200 mL of diethyl ether.
  • the suspension was filtered and the resulting solid was washed 3 times with 50 mL of diethyl ether.
  • the white solid was finally washed 2 times with 50 mL of methanol and was dried under vacuum to remove traces of solvent.
  • the purified yield was 44%.
  • Adsorption of cationic surfactant on negatively charged surface is an important property for various applications. This property is linked to the minimal concentration of cationic surfactant needed to produce aggregation of negatively charged cellulose nano crystal (CNC) in suspension in aqueous media. Comparison of the aggregate size can be monitored by dynamic light scattering (DLS).
  • DLS dynamic light scattering
  • the range of CNC aggregation correspond to the range of ratio X (or M) triggering an aggregation of CNC, i.e. the range where the aggregate size measured by DLS is higher than a pure aqueous solution of CNC or an aqueous solution of surfactant at 0.01wt%.
  • Ranges of X and M of aggregation of CNC are summarized in Table 1.
  • Table 1 Range of CNC aggregation (ratio) X [surfactant]/[CNC] X min - X max Range of CNC aggregation (mass fraction) M min - M max Compound of example 3 0.1-1.82 0.09-0.65 Fentacare ® TEP 1-33 0.50-0.97
  • Fentacare ® TEP was used as a comparison.
  • Fentacare ® TEP is a commercial surfactant representing the benchmark.
  • Biodegradability of the test substances has been measured according to the 301 F OECD protocol.
  • Oxitop TM respirometric bottles were used in this test in order to access the biodegradability of the test samples: sealed culture BOD flasks were used at a temperature of 20 ⁇ 2 C during 28 days.
  • Evolved carbon dioxide was absorbed by pellets of Natrium or Potassium hydroxide present in the head space of the bottle.
  • Inoculum corresponded to a municipal activated sludge washed in mineral medium (ZW media) in order to decrease the DOC (Dissolved Oxygen Carbon) content.
  • Control solutions containing the reference substance sodium acetate and also toxicity control (test substance + reference substance) were used for validation purposes.
  • Toxicity control corresponds to the mixture of the substance reference and the test substance; it will check if the test substance is toxic towards the inoculum (if so, the test has to be redone at a lower test substance concentration, if feasible regarding the sensitivity of the method).
  • the substances of the present invention are for a majority of them not very soluble in water (if some are soluble in water, their metabolite after hydrolysis containing the alkyl chain has often very low solubility in water), we used a specific protocol named the "emulsion protocol”. This protocol enabled us to increase the bioavailability of the poorly water soluble substance in the aqueous phase where we had the inoculum.
  • Emulsion protocol consisted of adding the test substance in the bottle through a stock solution made in an emulsion.
  • Emulsion was a 50/50 v/v mixture of a stock solution of the test substance dissolved in a non-biodegradable surfactant (Synperonic ® PE 105 at 1 g/l) and then mixed with a mineral silicone oil AR 20 (Sigma).
  • a non-biodegradable surfactant Synperonic ® PE 105 at 1 g/l
  • the first dissolution of the test substance in the non-biodegradable surfactant solution often required magnetic stirrer agitation followed by ultrasonication.
  • Two emulsion controls were run in parallel during the test in order to remove their value from the emulsion bottle containing the test substance added through the emulsion stock solution.
  • the ionic compounds of the present invention show a good combination of surfactant properties combined with a good biodegradabilty, a combination which is in many cases not achieved by commercial surfactants.
  • the compounds of the present invention are also easily available starting from internal ketones which are easily accessible from fatty acids or fatty acid derivatives, the compounds of the present invention also provide economical benefits over the prior art compounds.

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EP20189198.3A 2020-08-03 2020-08-03 Neues verfahren zur gewinnung von diesterverbindungen, die zur herstellung neuer quartärer ammoniumverbindungen nützlich sind Withdrawn EP3950663A1 (de)

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EP4165012A1 (de) * 2020-06-16 2023-04-19 Rhodia Operations Neue ammoniumverbindungen als tenside

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